Silicone polymer emulsions

ABSTRACT

Silicone oil-in-water emulsions containing a polysiloxane containing polymer is prepared by first preparing a polysiloxane containing polymer by the polymerisation of siloxane containing monomers and/or oligomers in the presence of an inert organopoly siloxane and/or an organic fluid, a suitable catalyst and optionally an end-blocking agent; and quenching the reaction if required. If required one or more surfactants may be introduced into the polysiloxane containing polymer to form a homogenous oil phase. Water is then added (in an amount of 0.1-10 percent by weight based on total oil phase weight) to the homogenous oil phase to form a water-in-oil emulsion. Shear is applied to the water-in-oil emulsion to cause inversion of the water-in-oil emulsion to an oil-in-water emulsion. Finally, if required the oil-in-water emulsion can be diluted by adding more water.

This invention relates to silicone in water emulsions, methods of makingsaid emulsions and their uses.

Silicone emulsions are well known in the art. Such silicone emulsionscan be made by processes such as (i) mechanical emulsification, (ii)mechanical emulsification by inversion, or by (iii) emulsionpolymerization. However, because of the high viscosity of some siliconessuch as silicone gums, their emulsification has for all practicalpurposes been limited to emulsion polymerization. In contrast, siliconeswith a low viscosity and hence a low molecular weight can easily beobtained mechanically.

Attempts to use mechanical methods for emulsifying high molecular weightand viscosity organopolysiloxane polymers, often referred to as siliconegums, have largely been unsuccessful, because it is difficult toincorporate a surfactant or a mixture of surfactants into the polymerbecause of the viscosity of the polymer. It is also difficult toincorporate water into mixtures containing high viscosity silicones, asurfactant, or a mixture of surfactants, and at the same time impartsufficient shear to cause inversion. In addition, the control ofparticle size has been limited to processes involving batch-wisemechanical emulsification in the presence of a volatile solvent which issubstantially removed during the polymerisation process.

In contrast to the above, the present invention provides an inexpensivetechnique for producing stable emulsions comprising silicone polymersincluding polymers which if traditionally prepared would have theviscosity of a silicone gum or like high viscosity polymers.

Whilst the present application relates to organopolysiloxane polymershaving a viscosity when prepared traditionally of greater than 50 000mPa·s at 25° C. being used to prepare emulsions it is consideredparticularly pertinent to organopolysiloxane polymers of very highviscosity, known in the industry as Silicone gums (e.g. viscosity ofabout 1 000 000 mPa·s at 25° C. or greater). Silicone gums are highmolecular weight generally linear or branched polydiorganosiloxanes thatcan be converted from their highly viscous plastic state into apredominately elastic state by crosslinking. Silicone gums are oftenused as one of the main components in the preparation of siliconeelastomers and silicone rubbers.

For purposes of this invention therefore, silicone gum can be consideredto describe stiff gum-like organosiloxane polymer having a degree ofpolymerisation equal to or greater than 1500. These polymers arepreferably substantially linear, most preferably completely linear andhave a viscosity which is sufficiently high to render direct viscosityvery difficult and as such are often referred to in terms of theirWilliams plasticity number. Gums typically have a Williams plasticitynumber (ASTM D926) in the range of from about 30 to 250 (the thicknessin millimetres×100 of a cylindrical test specimen 2 cubic cm in volumeand approximately 10 mm in height after the specimen has been subjectedto a compressive load of 49 Newtons for three minutes at 25° C.

The two main routes to emulsifying high molecular weight silicones areemulsion polymerisation or the dilution of pre-formed high molecularweight polymers with low molecular weight silicone fluids such as cyclicsiloxanes comprising between 2 and 20 silicon atoms. Proceeding downeither of these routes can lead to a number of processing problems whichare extremely difficult to overcome. In the case of emulsionpolymerisation it is exceptionally difficult to control the molecularweight of the end product and indeed viscosities resulting from suchprocesses are so high that there is typically no absolute means ofmeasuring the viscosity of the product manufactured via this route. Itis also difficult to achieve a truly continuous process. Pre-formedsiloxane polymers having very high viscosities (viscosity greater than 1000 000 mPa·s at 25° C.) are very difficult to dilute because it is verydifficult to get lower weight compounds to blend in to the highmolecular weight polymer.

U.S. Pat. No. 5,973,068 discusses the emulsion polymerisation of asilanol-terminated resin and a vinyl monomer. Polymerization in theemulsion polymerization process occurs at the silicone water interfaceso that the rate of polymerization is faster with smaller particlesbecause of the larger surface area. Thus, it is impossible to producelarge particle size, high molecular weight silicone gum in wateremulsions by emulsion polymerisation.

EP1646696 describes a method of making a silicone oil-in-water emulsioncomprising the steps of forming a homogeneous oil phase containing asilicone gum, or the like in the homogenous oil phase mixing one or moresurfactants with the homogenous oil phase; adding water to thehomogenous oil phase to form a water-in-oil emulsion containing acontinuous phase and a dispersed phase, the water being added in anamount of about 0.5-10 percent by weight based on the weight of thesilicone in the homogenous oil phase; applying high shear to thewater-in-oil emulsion in a twin-screw extruder having a length todiameter L/D ratio of at least 15, to cause inversion of thewater-in-oil emulsion to an oil-in-water emulsion; and diluting theoil-in-water emulsion by the addition of water.

EP1447423 describes a process for the production of a silicone in wateremulsion in which a polysiloxane fluid, at least one surfactant andwater are continuously fed to a high shear mixer in such proportions asto form a viscous oil in water emulsion which is continuously withdrawnfrom the mixer. The polysiloxane fluid may be a non-reactive fluid ormay have reactive groups capable of taking part in a chain extensionreaction.

The invention is directed to a method of making silicone oil-in-wateremulsions containing a polysiloxane containing polymer comprising thesteps of

-   i) Preparing a polysiloxane containing polymer by the polymerisation    of siloxane containing monomers and/or oligomers in the presence of    an inert organopolysiloxane and/or an organic fluid, a suitable    catalyst and optionally an end-blocking agent; and-   ii) Where required quenching the polymerisation process; wherein the    inert fluid is substantially retained within the resulting diluted    polysiloxane containing polymer-   (iii) if required, introducing one or more surfactants into the    polysiloxane containing polymer to form a homogenous oil phase;-   (iv) adding water to the homogenous oil phase to form a water-in-oil    emulsion containing a continuous phase and a dispersed phase,-   (v) applying shear to the water-in-oil emulsion to cause inversion    of the water-in-oil emulsion to an oil-in-water emulsion; and    optionally-   (vi) diluting the oil-in-water emulsion by adding more water.

The concept of “comprising” where used herein is used in its widestsense to mean and to encompass the notions of “include” and “consistof”. All viscosity measurements referred to herein were measured at 25°C. unless otherwise indicated.

For the sake of this application an inert fluid a substantiallynon-volatile fluid which is intended to be unreactive towards any otherconstituent i.e. it does not chemically participate in thepolymerisation reaction of step (i) or chemically interact with theadditives introduced in any of steps (i) through to (vi). The inertfluid is not removed prior to emulsification. Hence the inert fluid issubstantially present in the emulsion.

A polysiloxane containing polymer is intended to mean a polymercomprising multiple organosiloxane or polyorganosiloxane groups permolecule and is intended to include a polymer substantially containingonly organosiloxane or polyorganosiloxane groups in the polymer chainand polymers where the backbone contains both organosiloxane and/orpolyorganosiloxane groups and e.g. organic polymeric groups in thepolymeric chain. Such polymers can be homopolymers or co-polymers,including, but not limited to, block co-polymers and random co-polymers.

In accordance with the present invention a polysiloxane containingpolymer is polymerised in the presence of an inert fluid preferably hasthe general formula:

R_((3-a))R¹ _(a)SiO[(R₂SiO)_(b)(RR¹SiO)_(c)]SiR_((3-a))R¹ _(a)  (1)

wherein each R is the same or different and is an alkyl group containing1-8 carbon atoms, a substituted alkyl group containing 1 to 6 carbonatoms or an optionally substituted phenyl group; R¹ is hydrogen, ahydroxy group, a hydrolysable group, an unsaturated organic group; a iszero or 1, b is an integer and c is zero or an integer and the sum ofb+c is equal to a value of at least 200 preferably at least 500, morepreferably at least 1500. Such a polymer may comprise a degree ofbranching (preferably less than 10%, more preferably less that 2%).

For the purpose of this application “Substituted”, when used in relationto hydrocarbon groups, means one or more hydrogen atoms in thehydrocarbon group has been replaced with another substituent. Examplesof such substituents include, but are not limited to, halogen atoms suchas chlorine, fluorine, bromine, and iodine; halogen atom containinggroups such as chloromethyl, perfluorobutyl, trifluoroethyl, andnonafluorohexyl; oxygen atoms; oxygen atom containing groups such as(meth)acrylic and carboxyl; nitrogen atoms; nitrogen atom containinggroups such as amines, amino-functional groups, amido-functional groups,and cyano-functional groups; sulphur atoms; and sulphur atom containinggroups such as mercapto groups.

The polymeric chain may comprise blocks made from chains of unitsdepicted in Formula (1) above where the two R groups or R and R¹ groupsare:—

-   -   both alkyl groups (preferably both methyl or ethyl), or    -   alkyl and phenyl groups, or    -   alkyl and fluoropropyl, or    -   alkyl and vinyl or    -   alkyl and hydrogen groups.        Typically at least one block will comprise siloxane units in        which both R groups are alkyl groups.

Whilst preferably the polysiloxane containing polymer has asubstantially organopolysiloxane molecular chain, the polysiloxanecontaining polymer may alternatively contain a block copolymericbackbone comprising at least one block of siloxane groups and an organiccomponent comprising any suitable organic based polymer backbone forexample the organic polymer backbone may comprise, for example,polystyrene and/or substituted polystyrenes such aspoly(α-methylstyrene), poly(vinylmethylstyrene), dienes,poly(p-trimethylsilylstyrene) andpoly(p-trimethylsilyl-α-methylstyrene). Other organic components whichmay be incorporated in the polymeric backbone may include acetyleneterminated oligophenylenes, vinylbenzyl terminated aromaticpolysulphones oligomers, aromatic polyesters; aromatic polyester basedmonomers, polyalkylenes, polyurethanes, aliphatic polyesters, aliphaticpolyamides and aromatic polyamides and the like.

However perhaps the most preferred organic based polymeric blocks inpolysiloxane containing polymer are polyoxyalkylene based blocks. Theoxyalkylene units are not necessarily identical throughout thepolyoxyalkylene monomer, but can differ from unit to unit. Apolyoxyalkylene block, for example, can be comprised of oxyethyleneunits, (—C₂H₄—O—); oxypropylene units (—C₃H₆—O—); or oxybutylene units,(—C₄H₈—O—); or mixtures thereof. Preferably the polyoxyalkylenepolymeric backbone consists essentially of oxyethylene units and/oroxypropylene units.

Other polyoxyalkylene blocks in the polysiloxane containing polymer mayinclude for example units of the structure—

-[—R²—O—(—R³—O—)_(d)—Pn—C(R⁴)₂—Pn—O—(—R³—O—)_(e)—R²]—

in which Pn is a 1,4-phenylene group, each R² is the same or differentand is a divalent hydrocarbon group having 2 to 8 carbon atoms, each R³is the same or different and, is, an ethylene group propylene group orisopropylene group, each R⁴ is the same or different and is a hydrogenatom or methyl group and each of the subscripts d and e is a positiveinteger in the range from 3 to 30.

Preferably the inert fluid is selected from an organopolysiloxaneextender and/or plasticiser and/or an organic extender or plasticiser ora cyclic siloxane comprising between 3 and 20 silicon atoms. Preferablythe inert fluid has a viscosity of from 0.65 mPa·s at 25° C.—10000 mPa·sat 25° C.

For the sake of this application an extender (sometimes also referred toas a process aid or secondary plasticiser) is a compound typically usedto dilute e.g. silicone based product to make the product moreeconomically competitive without substantially negatively affecting theproperties of the sealant formulation.

A plasticiser (otherwise referred to as a primary plasticiser) is addedto silicone based compositions to provide properties within the finalpolymer based product to increase the flexibility and toughness of curedelastomers. This is generally achieved by reduction of the glasstransition temperature (T_(g)) of the cured polymer composition therebye.g. enhancing the elasticity of the elastomer (e.g. a sealant).Plasticisers tend to be generally less volatile than extenders.

Suitable inert liquids include trialkylsilyl terminatedpolydialkylsiloxanes and derivatives thereof which may comprise a degreeof substitution, with the provision that any substituted groups in theinert fluid do not participate in the polymerisation reaction. Thesubstituted groups on the inert fluid are preferably the same as thoseidentified in the previous definition of substituted groups with respectto hydrocarbon groups. Preferably each alkyl group may be the same ordifferent and comprises from 1 to 8 carbon atoms but is preferably amethyl or ethyl group, preferably with a viscosity of from 0.65 to 100000 mPa·s at 25° C. and most preferably from 10 to 1000 mPa·s at 25° C.

The inert fluid may comprise any suitable organic extender/organicplasticiser. Mineral oil extenders and plasticisers are howeverparticularly preferred. Examples include linear or branched monounsaturated hydrocarbons such as linear or branched alkenes or mixturesthereof containing at least 12, e.g. from 12 to 25 carbon atoms; and/ormineral oil fractions comprising linear (e.g. n-paraffinic) mineraloils, branched (iso-paraffinic) mineral oils, cyclic (referred in someprior art as naphthenic) mineral oils and mixtures thereof. Preferablythe hydrocarbons utilised comprise at least 10, preferably at least 12and most preferably greater than 20 carbon atoms per molecule.

Other preferred mineral oil extenders include alkylcycloaliphaticcompounds, low molecular weight polyisobutylenes, Phosphate esters,alkybenzenes including polyalkylbenzenes which are unreactive with thepolymer.

Any suitable mixture of mineral oil fractions may be utilised as theextender in the present invention but high molecular weight extenders(e.g. >220) are particularly preferred. Examples include:—

alkylcyclohexanes (molecular weight >220);paraffinic hydrocarbons and mixtures thereof containing from 1 to 99%,preferably from 15 to 80% n-paraffinic and/or isoparaffinic hydrocarbons(linear branched paraffinic) and 1 to 99%, preferably 85 to 20% cyclichydrocarbons (naphthenic) and a maximum of 3%, preferably a maximum of1% aromatic carbon atoms. The cyclic paraffinic hydrocarbons(naphthenics) may contain cyclic and/or polycyclic hydrocarbons. Anysuitable mixture of mineral oil fractions may be used, e.g. mixturescontaining

-   (i) 60 to 80% paraffinic and 20 to 40% naphthenic and a maximum of    1% aromatic carbon atoms;-   (ii) 30-50%, preferably 35 to 45% naphthenic and 70 to 50%    paraffinic and or isoparaffinic oils;-   (iii) hydrocarbon fluids containing more than 60 wt. % naphthenics,    at least 20 wt. % polycyclic naphthenics and an ASTM D-86 boiling    point of greater than 235° C.;-   (iv) hydrocarbon fluid having greater than 40 parts by weight    naphthenic hydrocarbons and less than 60 parts by weight paraffinic    and/or isoparaffinic hydrocarbons based on 100 parts by weight of    hydrocarbons.

Preferably the mineral oil based extender or mixture thereof comprisesat least one of the following parameters:—

-   (i) a molecular weight of greater than 150, most preferably greater    than 200;-   (ii) an initial boiling point equal to or greater than 230° C.    (according to ASTM D 86).-   (iii) a viscosity density constant value of less than or equal to    0.9; (according to ASTM 2501)-   (iv) an average of at least 12 carbon atoms per molecule, most    preferably 12 to 30 carbon atoms per molecule;-   (v) an aniline point equal to or greater than 70° C., most    preferably the aniline point is from 80 to 110° C. (according to    ASTM D 611);-   (vi) a naphthenic content of from 20 to 70% by weight of the    extender and a mineral oil based extender has a paraffinic content    of from 30 to 80% by weight of the extender according to ASTM D    3238);-   (vii) a pour point of from −50 to 60° C. (according to ASTM D 97);-   (viii) a kinematic viscosity of from 1 to 20 cSt at 40° C.    (according to ASTM D 445)-   (ix) a specific gravity of from 0.7 to 1.1 (according to ASTM    D1298);-   (x) a refractive index of from 1.1 to 1.8 at 20° C. (according to    ASTM D 1218)-   (xi) a density at 15° C. of greater than 700 kg/m³ (according to    ASTM D4052) and/or-   (xii) a flash point of greater than 100° C., more preferably greater    than 110° C. (according to ASTM D 93)-   (xiii) a saybolt colour of at least +30 (according to ASTM D 156)-   (xiv) a water content of less than or equal to 250 ppm-   (xv) a Sulphur content of less than 2.5 ppm (according to ASTM D    4927)

Other organic extenders may include for the sake of example, fatty acidsand fatty acid esters, alkylbenzene compounds suitable for use includeheavy alkylate alkylbenzene or an alkylcycloaliphatic compound. Examplesof alkyl substituted aryl compounds useful as extenders and/orplasticisers are compounds which have aryl groups, especially benzenesubstituted by alkyl and possibly other substituents, and a molecularweight of at least 200.

The alkylbenzene compounds suitable for use include heavy alkylatealkylbenzene or an alkylcycloaliphatic compound. Examples of alkylsubstituted aryl compounds useful as extenders and/or plasticisers arecompounds which have aryl groups, especially benzene substituted byalkyl and possibly other substituents, and a molecular weight of atleast 200. Examples of such extenders are described in U.S. Pat. No.4,312,801, the content of which is incorporated herein by reference.These compounds can be represented by general formula (2), (3), (4) and(5):—

where R⁶ is an alkyl chain of from 1 to 30 carbon atoms, each of R⁷through to R¹⁶ is independently selected from hydrogen, alkyl, alkenyl,alkynyl, halogen, haloalkyl, nitrile, amine, amide, an ether such as analkyl ether or an ester such as an alkyl ester group, and n is aninteger of from 1 to 25.

Of these formula (2) where each of R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is hydrogenand R⁶ is a C₁₀-C₁₃ alkyl group. A particularly useful source of suchcompounds are the so-called “heavy alkylates”, which are recoverablefrom oil refineries after oil distillation. Generally distillation takesplace at temperatures in the range of from 230 to 330° C., and the heavyalkylates are present in the fraction remaining after the lighterfractions have been distilled off.

Examples of alkylcycloaliphatic compounds are substituted cyclohexaneswith a molecular weight in excess of 220. Examples of such compounds aredescribed in EP 0842974, the content of which is incorporated herein byreference. Such compounds may be represented by general formula (6).

where R¹⁷ is a straight or branched alkyl group of from 1 to 25 carbonatoms, and R¹⁸ and R¹⁹ are independently selected from hydrogen or aC₁₋₂₅ straight or branched chain alkyl group.

Alternatively the inert fluid may comprise may comprise a suitablenon-mineral based natural oil or a mixture thereof, i.e. those derivedfrom animals, seeds and nuts and not from mineral oils (i.e. not frompetroleum or petroleum based oils) such as for example almond oil,avocado oil, beef tallow, borrage oil, butterfat, canola oil, cardanol,cashew nut oil, cashew nutshell liquid, castor oil, citrus seed oil,cocoa butter, coconut oil, cod liver oil, corn oil, cottonseed oil,cuphea oil, evening primrose oil, hemp oil, jojoba oil, lard, linseedoil, macadamia oil, menhaden oil, oat oil, olive oil, palm kernel oil,palm oil peanut oil, poppy seed oil, rapeseed oil, rice bran oil,safflower oil, safflower oil (high oleic), sesame oil, soybean oil,sunflower oil, sunflower oil (high oleic), tall oil, tea tree oil,turkey red oil, walnut oil perilla oil, dehydrated castor oils, apricotoil, pine nut oil, kukui nut oil, amazon nut oil almond oil, babasu oil,argan oil, black cumin oil, bearberry oil, calophyllum oil, camelinaoil, carrot oil, carthamus oil, cucurbita oil, daisy oil, grape seedoil, foraha oil, jojoba oil, queensland oil, onoethera oil, ricinus oil,tamanu oil, tucuma oil, fish oils such as pilchard, sardine and herringoils. The extender may alternatively comprise mixtures of the aboveand/or derivatives of one or more of the above.

A wide variety of natural oil derivates are available. These includetransesterified natural vegetable oils, boiled natural oils such asboiled linseed oil, blown natural oils and stand natural oils. Anexample of a suitable transesterified natural vegetable oil is known asbiodiesel oil, the transesterification product produced by reactingmechanically extracted natural vegetable oils from seeds, such as rape,with methanol in the presence of a sodium hydroxide or potassiumhydroxide catalyst to produce a range of esters dependent on the feedutilised. Examples might include for example methyloleate(CH₃(CH₂)₇CH═CH(CH₂)₇CO₂CH₃).

Stand natural oils which are also known as thermally polymerised or heatpolymerised oils and are produced at elevated temperatures in theabsence of air. The oil polymerises by cross-linking across the doublebonds which are naturally present in the oil. The bonds are of thecarbon-carbon type. Stand oils are pale coloured and low in acidity.They can be produced with a wider range of viscosities than blown oilsand are more stable in viscosity. In general, stand oils are producedfrom linseed oil and soya bean oil but can also be manufactured based onother oils. Stand oils are widely used in the surface coatings industry.

Blown oils which are also known as oxidised, thickened and oxidativelypolymerised oils and are produced at elevated temperatures by blowingair through the oil. Again the oil polymerises by cross-linking acrossthe double bonds but in this case there are oxygen moleculesincorporated into the cross-linking bond. Peroxide, hydroperoxide andhydroxyl groups are also present. Blown oils may be produced from awider range of oils than stand oils. In general, blown oils are darkerin colour and have a higher acidity when compared to stand oils. Becauseof the wide range of raw materials used, blown oils find uses in manydiverse industries, for example blown linseed oils are used in thesurface coatings industry and blown rapeseed oils are often used inlubricants.

The amount of inert fluid which may be included in the composition willdepend upon factors such as the purpose to which the composition is tobe put, the molecular weight of the inert fluid(s) concerned etc. Ingeneral however, the higher the molecular weight of the inert fluids(s),the less will be tolerated in the composition but such high molecularweight inert fluids have the added advantage of lower volatility.Typical compositions will contain up to 70% w/w inert fluids(s). Moresuitable polymer products comprise from 5-60% w/w of inert fluid(s).

Such polysiloxane containing polymers as prepared in step (i) of theprocess in accordance with the present invention may be made by avariety of routes with the polymers produced being end-capped withcompounds which will provide the required terminal groupings on thepolymer and provided the polymer or its precursors and/or intermediatesis/are diluted in the inert fluid described above during thepolymerisation process. Preferred routes to the preparation of saidpolymers include

(i) polycondensation(ii) ring opening/equilibrium(iii) polyaddition(iv) chain extension

(i) Polycondensation (i.e. the polymerisation of multiple monomersand/or oligomers with the elimination of low molecular weightby-product(s) such as water, ammonia or methanol etc.). Any suitablepolycondensation reaction pathway may be utilised.

The sort of reaction envisaged between the condensable end groups of thestarting materials are most preferably generally linked to theinteraction of compounds having hydroxyl and/or hydrolysable end groupswhich can interact with the release of e.g. water or methanol or thelike. However, the following list indicates other interactions whichmight be considered for the cure process of the composition inaccordance with the present invention:—

-   1) the condensation of organohalosilyl groups with an    organoalkoxysilyl groups,-   2) the condensation of organohalosilyl groups with    organoacyloxysilyl groups,-   3) the condensation of organohalosilyl groups with organosilanols,-   4) the condensation of organohalosilyl groups with silanolates,-   5) the condensation of organo-hydrosilyl groups with organosilanol    groups-   6) the condensation of organoalkoxysilyl groups with    organoacyloxysilyl groups-   7) the condensation of organoalkoxysilyl groups with organosilanol    groups,-   8) the condensation of organoaminosilyl groups with organosilanols,-   9) the condensation of organoacyloxysilyl groups silanolate groups-   10) the condensation of organoacyloxysilyl groups with    organosilanols,-   11) the condensation of organooximosilyl groups with organosilanol    groups-   12) the condensation of organoenoxysilyl groups with organosilanols,-   13) The condensation of a siloxane compound comprising one or more    hydrosilane functional groups with a siloxane compounds containing    at least one alkoxysilane functional group, generating hydrocarbon    by-products.

Most preferably the condensation reaction which occurs betweenmonomers/oligomers and intermediates with hydroxyl and/or alkoxyend-groups thereby producing water or alcohols as a by-product.

A preferred method for the polymerisation process is the polymerisationof straight chain precursors and/or branched organopolysiloxanes offormula (1) including for example

R_((3-f))R⁵ _(f)SiO(R₂SiO)_(g)SiR_((3-f))R⁵ _(f)

R_((3-f))R⁵ _(f)SiO(RR₁SiO)_(h)SiR_((3-f))R⁵ _(f)

R_((3-f))R⁵ _(f)SiO[(R₂SiO)_(j)(RR⁵SiO)_(k)]SiR_((3-f))R⁵ _(f)

Where R is as previously defined, R⁵ is —OH or an alkoxy group havingfrom 1 to 6 carbon atoms, preferably a methoxy or ethoxy group, f is 0or 1, preferably 1, g is an integer from 2 to 100, his from 2 to 100, jis an integer from 1 to 100 and k is an integer between 1 to 100. Somebranching may occur with the presence of other groups in the polymericchain but preferably this is kept to a minimum.

The above starting materials preferably have a viscosity of between 10mPa·s and 5000 mPa·s at 25° C.

Many of the above processes require the presence of catalyst. Anysuitable polycondensation catalyst may be utilised including tin, lead,antimony, iron, cadmium, barium, manganese, zinc, chromium, cobalt,nickel, titanium, aluminium, gallium or germanium and zirconium basedcatalysts such as organic tin metal catalysts and 2-ethylhexoates ofiron, cobalt, manganese, lead and zinc may alternatively be used.

Tin catalysts may include as triethyltin tartrate, tin octoate, tinoleate, tin naphthate, butyltintri-2-ethylhexoate, tinbutyrate,carbomethoxyphenyl tin trisuberate, isobutyltintriceroate, anddiorganotin salts especially diorganotin dicarboxylate compounds such asdibutyltin dilaurate, dimethyltin dibutyrate, dibutyltin dimethoxide,dibutyltin diacetate, dimethyltin bisneodecanoate Dibutyltin dibenzoate,stannous octoate, dimethyltin dineodeconoate, dibutyltin dioctoate.Dibutyltin dilaurate, dibutyltin diacetate are particularly preferred.

Titanate catalysts may comprise a compound according to the generalformula Ti[OR²⁰]₄ and Zr[OR²⁰]₄ respectively where each R²⁰ may be thesame or different and represents a monovalent, primary, secondary ortertiary aliphatic hydrocarbon group which may be linear or branchedcontaining from 1 to 10 carbon atoms. Optionally the titanate maycontain partially unsaturated groups. However, preferred examples of R²⁰include but are not restricted to methyl, ethyl, propyl, isopropyl,butyl, tertiary butyl and a branched secondary alkyl group such as2,4-dimethyl-3-pentyl. Preferably, when each R²⁰ is the same, R²⁰ is anisopropyl, branched secondary alkyl group or a tertiary alkyl group, inparticular, tertiary butyl. Examples include tetrabutyltitanate,tetraisopropyltitanate, or chelated titanates or zirconates such as forexample diisopropyl bis(acetylacetonyl)titanate, diisopropylbis(ethylacetoacetonyl)titanate, diisopropoxytitaniumBis(Ethylacetoacetate) and the like. Further examples of suitablecatalysts are described in EP1254192 and/or WO200149774 the contents ofwhich are incorporated herein by reference. The amount of catalyst useddepends on the cure system being used but typically is from 0.01 to 3%by weight of the total composition.

Other condensation catalysts which may be used, protic acids, Lewisacids, organic and inorganic bases, metal salts and organometalliccomplexes. Lewis acid catalysts. (a “Lewis acid” is any substance thatwill take up an electron pair to form a covalent bond) suitable for thepolymerisation in the present invention include, for example, borontrifluoride FeCl₃, AlCl₃, ZnCl₂, and ZnBr₂.

More preferred are condensation specific catalysts such as acidiccondensation catalysts of the formula R²¹SO₃H in which R²¹ represents analkyl group preferably having from 6 to 18 carbon atoms such as forexample a hexyl or dodecyl group, an aryl group such as a phenyl groupor an alkaryl group such as dinonyl- or didoecyl-naphthyl. Water mayoptionally be added. Preferably R²¹ is an alkaryl group having an alkylgroup having from 6 to 18 carbon atoms such as dodecylbenzenesulphonicacid (DBSA). Other condensation specific catalysts include n-hexylamine,tetramethylguanidine, carboxylates of rubidium or caesium, hydroxides ofmagnesium, calcium or strontium and other catalysts as are mentioned inthe art, e.g. in GB895091, GB918823 and EP 0382365. Also preferred arecatalysts based on phosphonitrile chloride, for example those preparedaccording to U.S. Pat. No. 3,839,388, U.S. Pat. No. 4,564,693 or EP215470 and phosphonitrile halide ion based catalysts, as described inGB2252975, having the general formula [X(PX₂═N)_(p)PX₃]⁺[M²_((m−n+1))R^(III) _(m)]⁻, wherein X denotes a halogen atom, M² is anelement having an electronegativity of from 1.0 to 2.0 according toPauling's scale, R^(III) is an alkyl group having up to 12 carbon atoms,p has a value of from 1 to 6, m is the valence or oxidation state of M²and n has a value of from 0 to m−1.

Alternatively the catalyst may comprise an oxygen-containingchlorophosphazene containing organosilicon radicals having the followinggeneral formula:—

Z¹—PCl₂═N(—PCl₂═N)_(q)—PCl₂—O

in whichZ¹ represents an organosilicon radical bonded to phosphorus via oxygen,a chlorine atom of the hydroxyl group andq represents 0 or an integer from 1 to 8. The catalyst may also comprisecondensation products of the above and/or tautomers thereof (thecatalyst exists in a tautomeric form when Z¹ is a hydroxyl group).

A further alternative catalyst which might be used as the catalyst inthe present invention is any suitable compound providing a source ofanions comprising at least one quadri-substituted boron atom and protonscapable of interaction with at least one silanol group as defined in WO01/79330.

The activity of the catalyst is preferably quenched by using aneutralizing agent which reacts with the catalyst to render itnon-active. Typically in the case of the acid type condensationcatalysts the neutralising agent is a suitable base such as an aminesuch as a mono/di and trialkanolamines for example monoethanolamine(MEA) and triethanolamine (TEA). In the case of systems using a DBSAcatalyst alternative quenching means include aluminasilicate zeolitematerials that were found to absorb DBSA and leave a stable polymer. Inmost cases catalyst residues remain in the polymer product or whereappropriate may be removed by filtration or alternative methods. In thecase of phosphazene based catalysts when the desired viscosity has beenreached, the viscosity of the organosilicon compound obtained in theprocess can be kept constant by a procedure in which the catalyst used,or a reaction product which has been formed from this catalyst byreaction with organosilicon compound to be subjected to condensationand/or equilibration and likewise promotes the condensation and/orequilibration of organosilicon compounds, is inhibited or deactivated byaddition of inhibitors or deactivators which have been employed to datein connection with phosphazenes, for example, triisononylamine,n-butyllithium, lithium siloxanolate, hexamethylcyclotrisilazane,hexamethyldisilazane and magnesium oxide.

Where appropriate any suitable end-blocking agent, which halts thepolymerization reaction and thereby limits the average molecular weight,may be used to introduce the appropriate end-groups in polymer (a).

(II) Equilibration/Ring Opening

The starting material for equilibration polymerisation processes such asring-opening polymerisation is a cyclosiloxane (also known as a cyclicsiloxane). Cyclic siloxanes which are useful are well known andcommercially available materials. They have the general formula(R²²SiO)_(r), wherein each R²² is selected from an alkyl group, analkenyl group, an aryl group or an aralkyl group and r denotes aninteger with a value of from 3 to 12. R²² can contain substitution, e.g.by halogen such as fluorine or chlorine. The alkyl group can be, forexample, methyl, ethyl, n-propyl, trifluoropropyl, n-butyl, sec-butyl,and tert-butyl. The alkenyl group can be, for example, vinyl, allyl,propenyl, and butenyl. The aryl and aralkyl groups can be, for example,phenyl, tolyl, and benzoyl. The preferred groups are methyl, ethyl,phenyl, vinyl, and trifluoropropyl. Preferably at least 80% of all R²²groups are methyl or phenyl groups, most preferably methyl. Preferablythe average value of r is from 3 to 6. Examples of suitable cyclicsiloxanes are octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane,decamethylcyclopentasiloxane, cyclopenta(methylvinyl)siloxane,cyclotetra(phenylmethyl)siloxane, cyclopentamethylhydrosiloxane andmixtures thereof. One particularly suitable commercially availablematerial is a mixture of comprising octamethylcyclotetrasiloxane anddecamethylcyclopentasiloxane. Typically moisture is present in themonomers. The water present acts as an end-blocker by forming OH endgroups on the polymers thereby preventing further polymerisation.

Any suitable catalyst may be used. These include alkali metal hydroxidessuch as lithium hydroxide, sodium hydroxide, potassium hydroxide orcaesium hydroxide, alkali metal alkoxides or complexes of alkali metalhydroxides and an alcohol, alkali metal silanolates such as potassiumsilanolate caesium silanolate, sodium silanolate and lithium silanolateor trimethylpotassium silanolate. Other catalysts which might beutilised include the catalyst derived by the reaction of a tetra-alkylammonium hydroxide and a siloxane tetramer and the boron based catalystsas hereinbefore described.

Catalysts which are most preferred for equilibrium type reactionshowever are phosphonitrile halides, phosphazene acids and phosphazenebases as hereinbefore described.

Where required the polymer obtained may be end-blocked as a means ofregulating the molecular weight of the polymer and/or to addfunctionality. Whilst this end-blocking function can be achieved bywater as discussed above, other suitable end-blocking agents includesilanes having one group capable of reacting with the terminal groups ofthe resulting polymeric constituent prepared in the diluted polymer toproduce the required end-groups for polymer (a).

(III) Polyaddition

For the sake of this specification a “polyaddition” or “additionpolymerisation” process is a polymerisation process whereby unlike in acondensation reaction no by-products such as water or alcohols aregenerated from the monomeric and oligomeric co-reactants duringpolymerisation. A preferred addition polymerisation route is ahydrosilylation reaction between an unsaturated organic group e.g. analkenyl or alkynyl group and an Si—H group in the presence of a suitablecatalyst. In this route suitable silanes may be utilised as well assiloxane containing monomers and/or oligomers.

Typically the polyaddition route is utilised to form block copolymers byreacting

-   a) (i) an organopolysiloxane or (ii) a silane with:—-   b) one or more organopolysiloxane polymer(s)    via an addition reaction pathway in the presence of the extender    and/or plasticiser, and a suitable catalyst and optionally an    end-blocking agent; and    where required quenching the polymerisation process.

The organopolysiloxane or silane (a) is selected from a silane (a) (ii)containing at least one group capable of undergoing addition typereactions and an organopolysiloxane monomer (a) (i) containing groupscapable of undergoing addition type reactions. The organopolysiloxane orsilane (a) must contain substituents such that it is capable ofundergoing an appropriate addition reaction with polymer (b). Thepreferred addition reaction is a hydrosilylation reaction between anunsaturated group and an Si—H group.

Preferably silane (a) (ii) has at least 1 and preferably 2 groupscapable of undergoing addition type reactions with (b). When theaddition reaction is a hydrosilylation reaction the silane may containan unsaturated constituent but preferably contains at least one Si—Hgroup. Most preferably each silane contains one or more Si—H groups. Inaddition to the one or more Si—H groups, preferred silanes may includefor example an alkyl group, an alkoxy group, an acyloxy group, aketoximato group, an amino group, an amido group, an acid amido group,an aminoxy group, a mercapto group, an alkenyloxy group and the like.Among these, alkoxy, acyloxy, ketoximato, amino, amido, aminoxy,mercapto and alkenyloxy groups are preferred. Practical examples of thesilicon hydride are halosilane tri-chlorosilane, methyl dichlorosilane,dimethyl chlorosilane, and phenyl dichlorosilane; alkoxy silanes, suchas tri-methyoxy silane, tri-ethoxy silane, methyl di-ethoxy silane,methyl di-methoxy silane and phenyl-di-methoxy silane; acyloxy silanes,such as methyl di-acetoxy silane and phenyl diacetoxy silane; andketoximato silanes, such as bis-(dimethyl-ketoximate)-methyl silane andbis-(cyclohexyl ketoximate)methyl silane. Among them, halosilanes andalkoxyl silanes are preferred. Particularly preferred silanes includefor example methyl dimethoxy silane (H—Si(—CH₃) (—OCH₃)₂).

It will be appreciated that the addition reaction between silane (a)(ii) and (b) results in a polymer chain extension process or as a meansof end-blocking a polymer with pre-required end groups, in which casethe extender may be added in combination with silane (a) (ii), i.e.immediately prior to the addition reaction or may be present during thepolymerisation of polymer (b) and as such silane (a) (ii) is added to anextended polymer (b) which has been polymerised in the presence of theextender.

Organopolysiloxane monomer (a) (i) is preferably in the form of astraight chain and/or branched organopolysiloxane comprising units offormula (1a)

R′_(a)—SiO_(4−a′/2)  (1a)

wherein each R′ may be the same or different and denotes a hydrocarbongroup having from 1 to 18 carbon atoms, a substituted hydrocarbon grouphaving from 1 to 18 carbon atoms or a hydrocarbonoxy group having up to18 carbon atoms and a′ has, on average, a value of froth 1 to 3,preferably 1.8 to 2.2. Preferably each R′ is the same or different andis exemplified by, but not limited to hydrogen, alkyl groups such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, andoctadecyl; cycloalkyl such as cyclohexyl; aryl such as phenyl, tolyl,xylyl, benzyl, and 2-phenylethyl; and halogenated hydrocarbon groupssuch as 3,3,3-trifluoropropyl, 3-chloropropyl, and dichlorophenyl. SomeR′ groups may be hydrogen groups. Preferably the polydiorganosiloxanesare polydialkylsiloxanes, most preferably polydimethylsiloxanes. When(a) is an organopolysiloxane monomer, said organopolysiloxane monomermust have at least one group which is reactable with at least twogroups, typically the terminal groups, of (b) via an addition reactionprocess. Preferably organopolysiloxane (a) (i) comprises at least oneSi—H per molecule, preferably at least two Si—H groups per molecule.Preferably organopolysiloxane (a) (i) is end-blocked with a siloxanegroup of the formula H(R″)₂SiO_(1/2), wherein each R″ is a hydrocarbonor substituted hydrocarbon group, most preferably an alkyl group.Preferably organopolysiloxane (a) (i) has a viscosity of between 10mPa·s and 5000 mPa·s at 25° C.

Organopolysiloxane polymer (b) is preferably a straight chain and/orbranched organopolysiloxane comprising units of formula (1b)

R′″_(a′)SiO_(4-a′/2)  (1b)

wherein each R′″ may be the same or different and denotes a hydrocarbongroup having from 1 to 18 carbon atoms, a substituted hydrocarbon grouphaving from 1 to 18 carbon atoms or a hydrocarbonoxy group having up to18 carbon atoms and a′ is as previously described. Preferably no R′″groups may be hydrogen groups. Preferably each R′″ is the same ordifferent and are exemplified by, but not limited to alkyl groups suchas methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl,and octadecyl; cycloalkyl such as cyclohexyl; aryl such as phenyl,tolyl, xylyl, benzyl, and 2-phenylethyl; and halogenated hydrocarbongroups such as 3,3,3-trifluoropropyl, 3-chloropropyl, anddichlorophenyl.

Organopolysiloxane polymer (b) may comprise any suitableorganopolysiloxane polymeric backbone but is preferably linear orbranched, and comprises at least one, preferably at least twosubstituent groups which will react with the aforementioned groups inthe organopolysiloxane or silane (a) via an addition reaction pathway.Preferably the or each addition reactive substituent group of polymer(b) is a terminal group. When the organopolysiloxane or silane (a)comprises at least one Si—H group, the preferred substituent groups onorganopolysiloxane polymer (b), which are designed to interact with theSi—H groups, are preferably unsaturated groups (e.g. alkenyl terminatede.g. ethenyl terminated, propenyl terminated, allyl terminated(CH₂═CHCH₂—)) or terminated with acrylic or alkylacrylic such asCH₂═C(CH₃)—CH₂— groups Representative, non-limiting examples of thealkenyl groups are shown by the following structures; H₂C═CH—,H₂C═CHCH₂—, H₂C═C(CH₃)CH₂—, H₂C═CHCH₂CH₂—, H₂C═CHCH₂CH₂CH₂—, andH₂C═CHCH₂CH₂CH₂CH₂—. Representative, non-limiting examples of alkynylgroups are shown by the following structures; HC≡C—, HC≡CCH₂—,HC≡CC(CH₃)—, HC≡CC(CH₃)₂—, HC≡CC(CH₃)₂CH₂— Alternatively, theunsaturated organic group can be an organofunctional hydrocarbon such asan acrylate, methacrylate and the like such as alkenyl an/or alkynylgroups. Alkenyl groups are particularly preferred.

In cases where the organopolysiloxane or silane (a) comprises only oneaddition reactable group and (b) comprises two addition reactable groupswhich will react with the organopolysiloxane or silane (a), theresulting product will be an “ABA” type polymeric product. Whereas whenboth the organopolysiloxane or silane (a) comprises two additionreactable groups and (b) comprises two addition reactable groups whichwill react with the organopolysiloxane or silane (a) interaction betweenthe two components would lead to (AB)n block copolymers in which thelength of the polymer is largely determined by the relative amounts ofthe two constituents.

It will also be appreciated that this hydrosilylation route may beutilised to prepare silicone-organic copolymers by using anorganopolysiloxane polymer which contains organic groups in the polymerbackbone or by replacing organopolysiloxane polymer (b) with, forexample alkenyl terminated polyethers Hence linear non-hydrolysable(AB)n block copolymers in accordance with the present invention of thisinvention can be prepared by catalyzed hydrosilylation of alkenylterminated polyethers with SiH-terminated dialkylsiloxane fluids. Theresulting copolymer being a combination of polyoxyalkylene blocks linkedthrough silicon to carbon to oxygen linkages (i.e. a propyleneoxy group)and the endblocking groups being selected from the group consisting ofallyl, propenyl and/or hydrogen (dialkyl) siloxy groups (dependent onthe relative amounts of the constituents which are present).

When the addition reaction chosen is a hydrosilylation reaction, anysuitable hydrosilylation catalyst may be utilised. Such hydrosilylationcatalysts are illustrated by any metal-containing catalyst whichfacilitates the reaction of silicon-bonded hydrogen atoms of the SiHterminated organopolysiloxane with the unsaturated hydrocarbon group onthe polyoxyethylene. The metals are illustrated by ruthenium, rhodium,palladium, osmium, iridium, or platinum.

Hydrosilylation catalysts are illustrated by the following;chloroplatinic acid, alcohol modified chloroplatinic acids, olefincomplexes of chloroplatinic acid, complexes of chloroplatinic acid anddivinyltetramethyldisiloxane, fine platinum particles adsorbed on carboncarriers, platinum supported on metal oxide carriers such as Pt(Al₂O₃),platinum black, platinum acetylacetonate,platinum(divinyltetramethyldisiloxane), platinous halides exemplified byPtCl₂, PtCl₄, Pt(CN)₂, complexes of platinous halides with unsaturatedcompounds exemplified by ethylene, propylene, and organovinylsiloxanes,styrene hexamethyldiplatinum, Such noble metal catalysts are describedin U.S. Pat. No. 3,923,705, incorporated herein by reference to showplatinum catalysts. One preferred platinum catalyst is Karstedt'scatalyst, which is described in Karstedt's U.S. Pat. Nos. 3,715,334 and3,814,730, incorporated herein by reference. Karstedt's catalyst is aplatinum divinyl tetramethyl disiloxane complex typically containing oneweight percent of platinum in a solvent such as toluene. Anotherpreferred platinum catalyst is a reaction product of chloroplatinic acidand an organosilicon compound containing terminal aliphaticunsaturation. It is described in U.S. Pat. No. 3,419,593, incorporatedherein by reference. Most preferred as the catalyst is a neutralizedcomplex of platinous chloride and divinyl tetramethyl disiloxane, forexample as described in U.S. Pat. No. 5,175,325.

Ruthenium catalysts such as RhCl₃(Bu₂S)₃ and ruthenium carbonylcompounds such as ruthenium 1,1,1-trifluoroacetylacetonate, rutheniumacetylacetonate and triruthinium dodecacarbonyl or a ruthenium1,3-ketoenolate may alternatively be used.

Other hydrosilylation catalysts suitable for use in the presentinvention include for example rhodium catalysts such as[Rh(O₂CCH₃)_(2]2), Rh(O₂CCH₃)₃, Rh₂(C₈H₁₅O₂)₄, Rh(C₅H₇O₂)₃,Rh(C₅H₇O₂)(CO)₂, Rh(CO)[Ph₃P](C₅H₁₇O₂), RhX⁴ ₃[(R³)₂S]₃, (R²₃P)₂Rh(CO)X⁴, (R² ₃P)₂Rh(CO)H, Rh₂X⁴ ₂Y⁴ ₄, H^(a)Rh^(b)olefin^(c)Cl^(d),Rh(O(CO)R³)_(3-n)(OH)_(n) where X⁴ is hydrogen, chlorine, bromine oriodine, Y⁴ is an alkyl group, such as methyl or ethyl, CO, C₈H₁₄ or 0.5C₈H₁₂, R³ is an alkyl radical, cycloalkyl radical or aryl radical and R²is an alkyl radical an aryl radical or an oxygen substituted radical, ais 0 or 1, b is 1 or 2, c is a whole number from 1 to 4 inclusive and dis 2, 3 or 4, n is 0 or 1. Any suitable iridium catalysts such asIr(OOCCH₃)₃, Ir(C₅H₇O₂)₃, [Ir(Z²)(En)₂]₂, or (Ir(Z²)(Dien)]₂, where Z²is chlorine, bromine, iodine, or alkoxy, En is an olefin and Dien iscyclooctadiene may also be used.

The hydrosilylation catalyst may be added to the present composition inan amount equivalent to as little as 0.001 part by weight of elementalplatinum group metal, per one million parts (ppm) of the composition.Preferably, the concentration of the hydrosilylation catalyst in thecomposition is that capable of providing the equivalent of at least 1part per million of elemental platinum group metal. A catalystconcentration providing the equivalent of about 3-50 parts per millionof elemental platinum group metal is generally the amount preferred.

Typically when (a) has at least two Si—H groups, typically, the processis carried out using approximately a 1:1 molar ratio of (a) to (b).However, useful materials may also be prepared by carrying out theprocess with an excess of either (a) or (b) but this would be considereda less efficient use of the materials. Typically, the materialcontaining the unsaturation (b) is used in slight excess to ensure allthe Si—H is consumed in the reaction. As polymer (b) used in the presentinvention is preferably terminated with unsaturated end-groups,end-blocking agents are not typically required when making the polymervia this route. However, they may be utilised if required.

Optionally when a hydrosilylation route is utilised for polymerisation asuitable hydrosilylation catalyst inhibitor may be required. Anysuitable platinum group type inhibitor may be used. One useful type ofplatinum catalyst inhibitor is described in U.S. Pat. No. 3,445,420,which is hereby incorporated by reference to show certain acetylenicinhibitors and their use. A preferred class of acetylenic inhibitors arethe acetylenic alcohols; especially 2-methyl-3-butyn-2-ol and/or1-ethynyl-2-cyclohexanol which suppress the activity of a platinum-basedcatalyst at 25° C. A second type of platinum catalyst inhibitor isdescribed in U.S. Pat. No. 3,989,667, which is hereby incorporated byreference to show certain olefinic siloxanes, their preparation andtheir use as platinum catalyst inhibitors. A third type of platinumcatalyst inhibitor includes polymethylvinylcyclosiloxanes having threeto six methylvinylsiloxane units per molecule.

Compositions containing these hydrosilylation catalysts typicallyrequire heating at temperatures of 70° C. or above to cure at apractical rate, particularly if an inhibitor is used. Room temperaturecure is typically accomplished with such systems by use of a two-partsystem in which the cross-linker and inhibitor are in one of the twoparts and the platinum is in the other part. The amount of platinum isincreased to allow for curing at room temperature. The optimumconcentration of platinum catalyst inhibitor is that which will providethe desired storage stability or pot life at ambient temperature withoutexcessively prolonging the time interval required to cure the presentcompositions at elevated temperatures. This amount will vary widely andwill depend upon the particular inhibitor that is used. Inhibitorconcentrations as low as one mole of inhibitor per mole of platinum willin some instances yield a desirable level of storage stability and asufficiently short curing period at temperatures above about 70° C. Inother cases, inhibitor concentrations of up to 10, 50, 100, 500 or moremoles per mole of platinum may be needed. The optimum concentration fora particular inhibitor in a given composition can be determined byroutine experimentation.

Additional components can be added to the hydrosilylation reaction whichare known to enhance such reactions. These components include salts suchas sodium acetate which have a buffering effect in combination withplatinum based catalysts.

For this type of polymerisation the amount of hydrosilylation catalystused is not narrowly limited as long as there is a sufficient amount toaccelerate a reaction between

-   -   (a) (i) an organopolysiloxane or (ii) a silane the chosen of        which must contain at least one and preferably at least two Si—H        groups with    -   (b) one or more organopolysiloxane polymer(s) or an alternative        therefore such as a polyoxyethylene having an unsaturated        hydrocarbon group at each molecular terminal at room temperature        or at temperatures above room temperature. The actual amount of        this catalyst will depend on the particular catalyst utilized        and is not easily predictable. However, for platinum-containing        catalysts the amount can be as low as one weight part of        platinum for every one million weight parts of components (a)        and (b). The catalyst can be added at an amount 10 to 120 weight        parts per one million parts of components (a) and (b), but is        typically added in an amount from 10 to 60 weight parts per one        million parts of (a) and (b).

Where appropriate, polymers obtained via a hydrosilylation route canalso be cured and/or crosslinked by a hydrosilylation reaction catalystin combination with an organohydrogensiloxane as the curing agentproviding each polymer molecule produced contains at least twounsaturated groups suitable for cross-linking with theorganohydrogensiloxane. To effect curing of the present composition, theorganohydrogensiloxane must contain more than two silicon bondedhydrogen atoms per molecule. The organohydrogensiloxane can contain, forexample, from about 4-20 silicon atoms per molecule, and have aviscosity of up to about 10 Pa-s at 25° C. The silicon-bonded organicgroups present in the organohydrogensiloxane can include substituted andunsubstituted alkyl groups of 1-4 carbon atoms that are otherwise freeof ethylenic or acetylenic unsaturation.

(IV) Chain Extension

In this case rather than adding chain extender into a final pre-preparedpolymer composition the extender is mixed into the polymer during achain extension polymerisation step. Typically the polymeric startingmaterial is an organopolysiloxane having end groups suitable forinteraction with the chosen chain extending materials. Typically thepolymer end groups are either hydrolysable or suitable for additionreaction (typically hydrosilylation) and the chain extending material ischosen on the basis of having suitable reactive groups which will chainextend the polymer. Preferred chain extending materials for chainextending polymers having hydroxyl and/or hydrolysable end groups are ashereinbefore described.

For pre-formed polymers with alkenyl or Si—H groups (typically endgroups) suitable for addition reactions via a hydrosilylation route thechain extender will contain two group which will undergo an additionreaction with the respective addition reactive groups on the chosenpolymer. Such chain extenders may include for example:—

A silane comprising two alkenyl groups, a dihydrosilane, apolydialkylsiloxane having a degree of polymerisation of from 2 to 25and at least one Si-alkenyl bond per terminal group, Apolydialkylsiloxane having a degree of polymerisation of from 2 to 25and at least one Si—H bond per terminal group and wherein each alkylgroup independently comprises from 1 to 6 carbon atoms;organosilicon compounds with the general formula

in which R is as hereinbefore described, j is 1, 2, or 3, k is 0 or 1,and j+k is 2 or 3.exemplified by compounds with the following formulas,(ViMe₂SiO)₂SiVi(OMe)₁ (ViMe₂SiO)₁SiVi(OMe)₂, (ViMe₂SiO)₂SiVi(OEt)₁,(ViMe₂SiO)₂SiVi(OEt)₂, (ViMe₂SiO)₃Si(OMe)₁, (ViMe₂SiO)₂Si(OMe)₂,(ViMe₂SiO)₃Si(OEt)₁ and (ViMe₂SiO)₂Si(OEt)₂As used herein, Vi represents a vinyl group, Me represents a methylgroup, and Et represents an ethyl group.

The catalyst used to catalyse the chain extension reaction is determinedby the reaction to take place. When the reaction occurring is acondensation reaction any suitable condensation catalyst as hereinbeforedescribed may be utilised. When the reaction occurring is ahydrosilylation reaction any suitable hydrosilylation catalyst ashereinbefore described may be utilised.

Where required the polymer contains hydrolysable terminal groups,end-blocking agents as described above in relation to condensation maybe utilised to obtain appropriate terminal groups. Where required thepolymer contains addition reactable terminal groups, end-blocking agentsas described above in relation to polyaddition may be utilised to obtainappropriate terminal groups.

The process can be carried out either batchwise or continuously on anysuitable mixers. In case of a polycondensation, generated water caneither be removed by chemical drying using e.g. hydrolysable silaneslike methyltrimethoxysilane or by physical separation using evaporation,coalescing or centrifuging techniques.

Chain extension may take place at any suitable temperature and pressurefor the process concerned in batch or continuous modes of operation aspreferred. Hence in the case of the phosphazene catalysed methodspolymerisation may occur at temperatures of between 50° C. to 200° C.,more preferably 80° C. to 160° C. Furthermore, in order to facilitateremoval of the by-products formed during the condensation, for example,water, HCl or alcohol, the condensation and/or equilibration of theorganosilicon compounds may be carried out at a pressure below 80 kPa.Alternative methods for the removal of condensation by-products includeremoval by chemical drying using e.g. hydrolysable silanes likemethyltrimethoxysilane (where appropriate) or by physical separationusing evaporation, coalescing or centrifuging techniques.

The process can be carried out either batchwise or continuously on anysuitable mixers. In case of a polycondensation, generated water caneither be removed by chemical drying using e.g. hydrolysable silaneslike methyltrimethoxysilane or by physical separation using evaporation,coalescing or centrifuging techniques.

Preferably the viscosity of the mixture of the polymer and inert fluidprior to emulsifying is in the range of viscosity of 1000-100000 mPa·sat 25° C. and preferably the viscosity of the polymer in the emulsion isgreater than 1 000 000 mPa·s at 25° C.

Any suitable surfactant or combination of surfactants may be utilised.The surfactant can in general be a non-ionic surfactant, a cationicsurfactant, an anionic surfactant, or an amphoteric surfactant, althoughnot all procedures for carrying out the process of the invention can beused with all surfactants. The amount of surfactant used will varydepending on the surfactant, but generally is up to about 30 wt. % basedon the polydiorganosiloxane.

Examples of nonionic surfactants include condensates of ethylene oxidewith long chain fatty alcohols or fatty acids such as a C₁₂₋₁₆ alcohol,condensates of ethylene oxide with an amine or an amide, condensationproducts of ethylene and propylene oxide, esters of glycerol, sucrose,sorbitol, fatty acid alkylol amides, sucrose esters, fluoro-surfactants,fatty amine oxides, polyoxyalkylene alkyl ethers such as polyethyleneglycol long chain (12-14C) alkyl ether, polyoxyalkylene sorbitan ethers,polyoxyalkylene alkoxylate esters, polyoxyalkylene alkylphenol ethers,ethylene glycol propylene glycol copolymers and alkylpolysaccharides,for example materials of the structure R²⁴—O—(R²⁵O)_(s)-(G)_(t) whereinR²⁴ represents a linear or branched alkyl group, a linear or branchedalkenyl group or an alkylphenyl group, R²⁵ represent an alkylene group,G represents a reduced sugar, s denotes 0 or a positive integer and trepresent a positive integer as described in U.S. Pat. No. 5,035,832.non ionic surfactants additionally include polymeric surfactants such aspolyvinyl alcohol (PVA) and polyvinylmethylether.

Representative examples of suitable commercially available nonionicsurfactants include polyoxyethylene fatty alcohols sold under thetradename BRIJ® by Uniqema (ICI Surfactants), Wilmington, Del. Someexamples are BRIJ® 35 Liquid, an ethoxylated alcohol known aspolyoxyethylene (23) lauryl ether, and BRIJ® 30, another ethoxylatedalcohol known as polyoxyethylene (4) lauryl ether. Some additionalnonionic surfactants include ethoxylated alcohols sold under thetrademark TERGITOL® by The Dow Chemical Company, Midland, Mich. Someexample are TERGITOL® TMN-6, an ethoxylated alcohol known as ethoxylatedtrimethylnonanol; and various of the ethoxylated alcohols, i.e., C₁₂-C₁₄secondary alcohol ethoxylates, sold under the trademarks TERGITOL®15-S-5; TERGITOL® 15-S-12, TERGITOL® 15-S-15, and TERGITOL® 15-S-40.Surfactants containing silicon atoms can also be used.

Examples of suitable amphoteric surfactants include imidazolinecompounds, alkylaminoacid salts, and betaines. Specific examples includecocamidopropyl betaine; cocamidopropyl hydroxysulfate, cocobetaine,sodium cocoamidoacetate, cocodimethyl betaine, N-coco-3-aminobutyricacid and imidazolinium carboxyl compounds. Representative examples ofsuitable amphoteric surfactants include imidazoline compounds,alkylaminoacid salts, and betaines.

Examples of cationic surfactants include quaternary ammonium hydroxidessuch as octyl trimethyl ammonium hydroxide, dodecyl trimethyl ammoniumhydroxide, hexadecyl trimethyl ammonium hydroxide, octyl dimethyl benzylammonium hydroxide, decyl dimethyl benzyl ammonium hydroxide, didodecyldimethyl ammonium hydroxide, dioctadecyl dimethyl ammonium hydroxide,tallow trimethyl ammonium hydroxide and coco trimethyl ammoniumhydroxide as well as corresponding salts of these materials, fattyamines and fatty acid amides and their derivatives, basic pyridiniumcompounds, quaternary ammonium bases of benzimidazolines andpolypropanolpolyethanol amines. Other representative examples ofsuitable cationic surfactants include alkylamine salts, sulphoniumsalts, and phosphonium salts.

Examples of suitable anionic surfactants include alkyl sulphates such aslauryl sulphate, polymers such as acrylates/C₁₀₋₃₀ alkyl acrylatecrosspolymer alkylbenzenesulfonic acids and salts such ashexylbenzenesulfonic acid, octylbenzenesulfonic acid,decylbenzenesulfonic acid, dodecylbenzenesulfonic acid,cetylbenzenesulfonic acid and myristylbenzenesulfonic acid; the sulphateesters of monoalkyl polyoxyethylene ethers; alkylnapthylsulfonic acid;alkali metal sulforecinates, sulfonated glyceryl esters of fatty acidssuch as sulfonated monoglycerides of coconut oil acids, salts ofsulfonated monovalent alcohol esters, amides of amino sulfonic acids,sulfonated products of fatty acid nitriles, sulfonated aromatichydrocarbons, condensation products of naphthalene sulfonic acids withformaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkylsulphates, ester sulphates, and alkarylsulfonates. Anionic surfactantsinclude alkali metal soaps of higher fatty acids, alkylaryl sulphonatessuch as sodium dodecyl benzene sulphonate, long chain fatty alcoholsulphates, olefin sulphates and olefin sulphonates, sulphatedmonoglycerides, sulphated esters, sulphonated ethoxylated alcohols,sulphosuccinates, alkane sulphonates, phosphate esters, alkylisethionates, alkyl taurates, and alkyl sarcosinates. One example of apreferred anionic surfactant is sold commercially under the nameBio-Soft N-300. It is a triethanolamine linear alkylate sulphonatecomposition marketed by the Stephan Company, Northfield, Ill.

The above surfactants may be used individually or in combination.

In a preferred embodiment of the present invention the polymerisationcatalyst is selected with a view to additionally being the or one of thesurfactants involved in the emulsification process. A particularlypreferred family of catalysts which can act as surfactants are acidiccondensation catalysts such as for example DBSA.

Phase inversions generally occurs when the continuous phase of adispersion becomes the dispersed phase, or vice versa. Phase inversionsin liquid/liquid dispersions generally are known in the art to beeffected by one of two methods. An inversion may be caused by changingthe phase ratio until there is a high enough ratio of the dispersedphase that it becomes the continuous phase. Alternatively, atransitional inversions may occur when the affinity of the surfactantfor the two phases is altered in order to cause the inversion.Typically, the inversions occurring in this invention occur due to achange in the phase ratio.

Thus, the inversion method used to make emulsions, according to theinvention, is carried out by forming an oil phase containing the dilutedpolysiloxane containing polymer and mixing and agitating the oil phase.A limited and very small amount of water is added to the oil phase in astepwise fashion, such that an inversion occurs, and an oil-in-wateremulsion is formed. Generally, the amount of water required is about0.5-10 percent by weight based on the cumulative weight of polysiloxanecontaining polymer present in the oil phase. Preferably, the amount ofwater will be about 1-5 percent by weight based on the weight of thepolysiloxane containing polymer present in the oil phase. While thewater can be added in 2-4 portions, addition of water in a singleportion is preferred. The initial addition of water can include thesurfactant. After the desired particle size has been reached, theemulsion is diluted with the balance of water to achieve the preferredsolids content.

The emulsions produced by the process of this invention can have a widevariety of polysiloxane containing polymer concentrations, particlesizes and molecular weights, including novel materials having highconcentrations of large particle polysiloxane containing polymer of highmolecular weight. The particle size can for example be chosen within therange 0.1 to 1000 micrometres.

The quantity of water and/or surfactant used in the initial phaseinversion process may have an impact on the particle size of the finalemulsion. For instance, if an emulsion is formed with the same quantityof water in two instances but in the first a large quantity of water ismixed before the phase inversion step and in the second a small quantityof water is mixed before the phase inversion step followed by mixing theremaining additional water after the phase inversion step, the firstemulsion will generally have a larger particle size than the second. Nomatter how the water is added, the total amount of water used isgenerally between about 1 and 99 wt. %, preferably between about 6 andabout 99 wt. %, based on the weight of the emulsion.

If desired, other materials can be added to either phase of theemulsions, for example perfumes, fillers, relaxers, colorants,thickeners, preservatives, or active ingredients such as pharmaceuticalsantifoams, freeze thaw stabilizers, inorganic salts to buffer pH, andthickeners

The emulsions of the present invention can generally have a siliconeloading in the range of about 1 to about 94 wt. %.

The emulsions of the invention are useful in most known applications forsilicone emulsions, for example in personal care applications such as onhair, skin, mucous membrane or teeth. In these applications, thesilicone is lubricious and will improve the properties of skin creams,skin care lotions, moisturisers, facial treatments such as acne orwrinkle removers, personal and facial cleansers such as shower gels,liquid soap, bar soaps hand sanitizers and wipes, bath oils, perfumes,fragrances, colognes, sachets, deodorants, sun protection creams,lotions, spray, stick and wipes, Self tanning creams, lotions, spray andwipes, pre-shave and after shave lotions, after sun lotion and creams,anti-perspirant sticks, soft solid and roll ons, hand sanitizers,shaving soaps and shaving lathers. It can likewise be use in hairshampoos, rinse-off and leave-on hair conditioners, hair styling aids,such as sprays, mousses and gels, hair colorants, hair relaxers,permanents, depilatories, and cuticle coats, for example to providestyling and conditioning benefits. In cosmetics, it function as alevelling and spreading agent for pigment in make-ups, colour cosmetics,compact gel, cream and liquid foundations (w/o and o/w emulsions,anhydrous), blushes, lipsticks, lip gloss, eye liners, eye shadows,mascaras, make up removers, colour cosmetic removers and powders. It islikewise useful as a delivery system for oil and water solublesubstances such as vitamins, fragrances, emollients, colorants, organicsunscreens, ceramides, pharmaceuticals and the like. When compoundedinto sticks, anhydrous and aqueous gels, o/w and w/o creams and lotions,aerosols and roll-ons, the emulsions of this invention impart a drysilky-smooth payout.

When used in personal care products, they are generally incorporated inamounts of about 0.01 to about 50 weight percent, preferably 0.1 to 25wt. percent, of the personal care product. They are added toconventional ingredients for the personal care product chosen. Thus,they can be mixed with deposition polymers, surfactants, detergents,antibacterials, anti-dandruffs, foam boosters, proteins, moisturisingagents, suspending agents, pacifiers, perfumes, colouring agents, plantextracts, polymers, and other conventional care ingredients.

Beyond personal care, the emulsion of the invention are useful fornumerous other applications such as paints, construction applications,textile fibre treatment, leather lubrication, fabric softening, fabriccare in laundry applications, healthcare, homecare, release agents,water based coatings, oil drag reduction, particularly in crude oilpipelines, lubrication, facilitation of cutting cellulose materials, andin many other areas where silicones are conventionally used. Thesilicone organic copolymers have particular advantages in oil dragreduction resulting from increased compatibility with hydrocarbonfluids.

EXAMPLES

The following Examples are provided so that one skilled in the art willmore readily understand the invention. Unless otherwise indicated, allparts and percents are by weight and all viscosities are at 25° C.Viscosity measurements of the polymer products were carried out using aBrookfield Viscometer, spindle 6, 10 rpm. All Particle size values weredetermined using a Malvern Mastersizer 2000.

Example 1

A polymer was prepared by polymerising 80 g of dimethyl hydroxylterminated polydimethylsiloxane having 71 mPa·s at 25° C. in 80 g oftrimethylsilyl terminated polydimethylsiloxane (PDMS) having a viscosityof 100 mPa·s at 25° C. using 2.4 g of dodecylbenzenesulphonic acid(DBSA) as catalyst for the condensation reaction. The polymerisation wasstopped once a viscosity of 10500 mPa·s at 25° C. was reached by theaddition of 1.12 g of Triethanolamine (TEA).

To 36 g of the above polymer the following surfactants were added, 1.1 gBrij® 30 and 1.9 g Brij® 35 L. These were added and mixed for 30 s at3000 rpm in Hausschild dental mixer. 1.2 g water was added and mixingwas repeated for 30 s at 3000 rpm. Another 0.4 g water was added and themixing was repeated again under the same conditions. After the secondwater addition the mixture had phase inverted and was diluted to apolymer content of 60%. The so obtained emulsion has a particle size ofD(v, 0.5) μm=0.81 and D(v, 0.9) μm=1.14. The emulsion remained intactfor a period of at least 6 months.

Brij® 30/Brij® 35 L are non-ionic polyoxyethylene fatty ether (POE)surfactants. Brij® 30 is POE(4) lauryl ether with a hydrophile-lipophilebalance (HLB) of 9.7. Brij® 35 L is a POE (23) lauryl ether with an HLBof 16.9.

Example 2

A polymer was prepared polymerising 128 g of dimethyl hydroxylterminated polydimethylsiloxane having a viscosity of 71 mPa·s at 25° C.in 32 g of PDMS having a viscosity of 100 mPa·s at 25° C. using 5.12 gof DBSA as the condensation catalyst. The polymerisation was stopped,once a viscosity of 171000 mPa·s at 25° C. was reached, by the additionof 2.39 g of TEA.

To 36 g of the above polymer the following surfactants were added, 1.1 gBrij® 30 and 1.9 g Brij® 35 L. These were added and mixed for 30 s at3000 rpm in Hausschild dental mixer. 0.5 g water was added mixing wasrepeated for 30 s at 3000 rpm. After mixing the mixture had phaseinverted and was diluted to a polymer content of 60%. The so obtainedemulsion has a particle size of D(v, 0.5) μm=1.77 and D(v, 0.9) μm=4.28.The emulsion remained intact for a period of at least 6 months.

Example 3

A polymer was prepared polymerising 128 g of dimethyl hydroxylterminated polydimethylsiloxane polydimethylsiloxane having a viscosityof 71 mPa·s at 25° C. in 32 g of PDMS 100 mPa·s at 25° C. using 4.48 gof DBSA. The polymerisation was stopped once a viscosity of 171000 mPa·sat 25° C. was reached by the addition of 2.09 g of TEA.

To 36 g of the above polymer the following two surfactants were added:1.3 g Brij® 30 and 2.4 g Brij® 35 L. The surfactants and polymer weremixed for 30 s at 3000 rpm in Hausschild dental mixer. After mixing themixture had phase inverted and was diluted to a polymer content of 60%.The so obtained emulsion has a particle size of D(v, 0.5) μm=2.07 andD(v, 0.9) μm=2.58. The emulsion remained intact for a period of at least6 months.

Example 4

To 36 g of the polymer prepared in example 3, were added the followingsurfactants, 2.25 g of Arquad 16-29 Arquad® 16-29 (Akzo Nobel) and 2.25g Tergitol®TMN-6 (Dow Chemical). No additional water was introduced asArquad® 16-29 contains 70% by weight of water and 2.25 g TMN-6 contains10% by weight of water. These were added and mixed for 30 s at 3000 rpmin Hausschild dental mixer. After mixing the mixture had phase invertedand was diluted to a polymer content of 60%. The so obtained emulsionhas a particle size of D(v, 0.5) μm=1.23 and D(v, 0.9) μm=1.7. Theemulsion remained intact for a period of at least 6 months.

Example 5

To 36 g of the polymer prepared in example 3 the following surfactantswere added, 2.25 g Arquad 16-29 and 2.25 g TMN-6 together with 0.5 gwater. These were mixed for 30 s at 3000 rpm in Hausschild dental mixer.After mixing the mixture had phase inverted and was diluted to a polymercontent of 60%. The so obtained emulsion has a particle size of D(v,0.5) μm=1.28 and D(v, 0.9) μm=1.96.

Arquad 16-29 is a cationic quaternary surfactant. TMN-6 is a non-ionicethoxylated alcohol with an HLB=13.1

Example 6

To 36 g of the polymer prepared in example 3 the following surfactantswere added, 1 g Biosoft N300 and 2 g Brij 30 (No additional wateradded). The surfactants were mixed with the polymer for 30 s at 3000 rpmin Hausschild dental mixer. After mixing the mixture had phase invertedand was diluted to a polymer content of 60%. The so obtained emulsionhas a particle size of D(v, 0.5) μm=2.14 and D(v, 0.9) μm=3.14

Example 7

A polymer was prepared polymerising a 1 to 1 mixture of dimethylhydroxyl terminated polydimethylsiloxane having a viscosity of 70 mPa·sat 25° C. and of an organic extender (Hydroseal G 250H (sold by Total)using 2.4% of DBSA as a catalyst. The polymerisation was stopped, by theaddition of 1.54% of TEA, once a viscosity of 40000 mPa·s at 25° C. wasreached.

To 40 g of the above polymer 1 g water was added and mixed for 30 s at3000 rpm in a Hausschild dental mixer. After mixing the mixture hadphase inverted. Additional 9 g water were added and mixing repeatedunder the same conditions. The mixture was then diluted to a polymercontent of 40%. The so obtained emulsion has a particle size of D(v,0.5) μm=1.46 and D(v, 0.9) μm=2.22

In this example no additional surfactant was required because thecondensation catalyst DBSA used in the preparation of the polymerfunctioned as the required surfactant.

Example 8

40 g of the polymer prepared in example 7 and 1 g water where mixed for30 s at 3000 rpm in Hausschild dental mixer. After mixing the mixturehad phase inverted. An additional 1 g water was then added and mixingrepeated under the same conditions. The mixture was then diluted to apolymer content of 50%. The so obtained emulsion has a particle size ofD(v, 0.5) μm=1.75 and D(v, 0.9) μm=2.76

In this example no additional surfactant was required because thecondensation catalyst DBSA used in the preparation of the polymerfunctioned as the required surfactant.

Example 9

A polymer was prepared by polymerising a 1:1 mixture of dimethylhydroxyl terminated polydimethylsiloxane having a viscosity of 70 mPa·sat 25° C. and of decamethylcyclopentasiloxane which has a viscosity of3.8 mPa·s at 25° C. using 2.4% of DBSA as a catalyst. The polymerisationwas stopped once a viscosity of 27000 mPa·s at 25° C. was reached by theaddition of 1.54% of TEA. In this case the DBSA catalyst used in thepolymerisation step above additionally functioned as the surfactant inthe preparation of emulsions as described below.

0.3 g water was added to 36 g of the above polymer and mixed for 30 s at3000 rpm in a Hausschild dental mixer. Another 0.9 g water weresubsequently added and mixed under the same conditions. After mixing themixture had phase inverted. A further 1.9 g of water was then added andmixing repeated under the same conditions. The resulting mixture wasthen diluted to a polymer content of 50%. The resulting emulsion has aparticle size of D(v, 0.5) μm=1.46 and D(v, 0.9) μm=2.34.

Example 10

A polymer was prepared by polymerising a 4:1 mixture of dimethylhydroxyl terminated polydimethylsiloxane having a viscosity of 70 mPa·sat 25° C. in an organic extender (Hydroseal G 250H) using 2.4% g of DBSAas a catalyst. The polymerisation was stopped once a viscosity of 40000mPa·s at 25° C. was reached by the addition of 1.54% g of TEA.

1 g water was added to 40.2 g of the above polymer and mixed for 30 s at3000 rpm in a Hausschild dental mixer. After mixing the mixture hadphase inverted. An additional 1.1 g of water was added and mixingrepeated under the same conditions. The resulting mixture was thendiluted to a polymer content of 50%. The so obtained emulsion has aparticle size of D(v, 0.5) μm=1.46 and D(v, 0.9) μm=2.26.

Example 11

1.1 g water was added and mixed with 40.2 g of the polymer prepared inExample 10 for 30 s at 3000 rpm in a Hausschild dental mixer. Aftermixing the resulting mixture had phase inverted. An additional 1.4 g ofwater was added and mixing repeated under the same conditions. A stillfurther 2.5 g of water was subsequently added and mixing repeated underthe same conditions. The resulting mixture was then diluted to a polymercontent of 80%. The resulting viscous cream (emulsion) had a particlesize of D(v, 0.5) μm=1.26 and D(v, 0.9) μm=1.84.

Example 12

A polymer was prepared by polymerising a 1:1 mixture of dimethylhydroxyl terminated polydimethylsiloxane having a viscosity of 70 mPa·sat 25° C. in cosmetic grade organic fluid (Isopar® M, sold by Exxon)using 20 parts per million (ppm) of a phosphonitrile catalyst. Thepolymerisation was stopped once a viscosity of 51000 mPa·s at 25° C. wasreached by the addition of trihexylamine. The polymer had a numberaverage molecular weight of 198000 g/mol and a polydispersity index of1.54.

1.1 g Volpo® L3, 1.6 g Volpo® L23 and 1.1 g water was added to 50.2 g ofthe polymer prepared as described above and the resulting mixture wasmixed for 60 s at 3000 rpm in a Hausschild dental mixer. An additional1.0 g of water was added and mixing repeated under the same conditions.A still further 1.0 g of water was added and the same mixing process wasrepeated again. After mixing the resulting mixture had phase inverted.Further 2.2 g of water was subsequently added and mixing repeated underthe same conditions. The resulting mixture was then diluted to apolymer/fluid content of 50%. The resulting emulsion had a particle sizeof D(v, 0.1) μm=1.23, D(v, 0.5) μm=2.67 and D(v, 0.9) μm=5.01 andhenceforth is referred to as sample 12.1 emulsion.

The resulting emulsion was introduced into a selection of personal careformulations, including fruity gel blushers, eye shadow, water in oilskin creams, hair care conditioners, leave-on and the following:—

Cold Mix Lotion

This lotion was prepared with the ingredients depicted in Table 12(a)below by initially mixing the phase B ingredients together and thenintroducing phase A into the phase B and then mixing the resultingproduct until it is homogeneous.

TABLE 12(A) Ingredients INCI Name % Phase A Sample 12.1 emulsion 20Phase B Water 78 Phenochem Phenoxyethanol (and) Methylparaben (and) 1Butylparaben (and) Ethylparaben (and) Propylparaben (and)Isobutylparaben Keltrol Xanthan Gum 1It was found that the sample 12.1 emulsion could be easily incorporatedin a lotion type product and the resulting lotion was found to have asignificant impact on sensory profile, in upon testing using 18panelists. Significant differences in >95% of results was found forspeed of absorption, gloss, film residue, greasiness. This indicatesthat sample 12.1 emulsion could significantly impact the sensory oflotion prepared as described herein, making it richer and morenourishing.

Water in Silicone Skin Cream

The above was prepared using the ingredients identified in Table 12(b)below:—

TABLE 12(B) Ingredients INCI Name % Phase A Dow Corning ®5225CCyclopentasiloxane (and) 10 Formulation Aid PEG/PPG-18/18 DimethiconeDow Corning ®245 Cyclopentasiloxane 18.6 Fluid Phase B Sample 12.1emulsion 2.3 Sodium Chloride 2 Water 67.1 Viscosity: Spindle 7, 20 rpm11800 mPa · s

The ingredients of phase A were mixed together. The ingredients of phaseB were mixed together. Phase B was then introduced dropwise into thephase A mixture whilst continuously agitation the resulting mixture andfinally the resulting mixture was homogenized using a high shear mixer.

Sensory tests were carried out using 18 panelists to determine theperformance of the resulting cream as described above, containing 2.3%by weight of Sample 12.1 emulsion in comparison to an identical cream inthe absence of the sample 12.1 emulsion. Significant differences >95%were identified with respect to speed of absorption, gloss, film residueand greasiness demonstrating that the presence of Sample 12.1 emulsionat levels as low as 2.3% impact significantly the sensory of the creammaking it richer and more nourishing.

Opaque Shampoo

The above was prepared using the ingredients identified in Table 12(c)below:—

TABLE 12(C) Ingredients INCI Name % Phase A Water 60.5 Crothix liquidPEG-150 Pentaerythrityl 1.5 Tetrastearate and PEG-6 Caprylic/CapricGlycerides and Water Empicol ESB-3 Sodium Laureth Sulfate 12 Texapon A400 Ammonium Lauryl Sulfate 10 Amonyl 380BA Cocamidopropyl Betaine 8Comperlan KD Cocamide DEA 4 Phase B Sample 12.1 emulsion 4 Phase CCitric Acid q.s Nipaguard DMDMH DMDM Hydantoin q.s Viscosity: Spindle 7,20 rpm 41600 mPa · s

Water was heated to 70° C. The ingredients of phase A were mixedtogether. Phase B was inter-mixed with phase A with gentle mixing andthen phase C was introduced and the resulting composition was allowed tocool.

Several panelists were asked to comb slightly bleached hair tresseswashed with the resulting shampoo. The time to wet detangle the hairtresses was measured. As a direct comparison the panelists alsoundertook the same process with slightly bleached hair tresses using thesame shampoo formulation without any emulsion. The results indicate aslight decrease in the detangling time with the shampoo containing thesample 12.1 emulsion. This indicates an improvement in the conditioningeffect in the shampoo when the emulsions in accordance with the presentinvention were present.

Example 13

A range of polymers Examples 13(a) to 13(i) were prepared bypolymerising mixtures of dimethyl hydroxyl terminatedpolydimethylsiloxane having a viscosity of 70 mPa·s at 25° C. andsunflower seed oil using DBSA as a catalyst (as indicated in Table13(a). All ingredients were mixed at 1500 rpm for 30 s (Hausschilddental mixer). The polymerisation was stopped after different times byadding TEA and mixing again under the same conditions.

TABLE 13A Example a b c d e f g h I Silox- 45 45 45 40 40 40 35 35 35ane (g) Sun- 5 5 5 10 10 10 15 15 15 flower Oil (g) DBSA 1.5 2 2.5 1.5 22.5 1.5 2 2.5 (g) TEA (g) 0.94 1.25 1.56 0.94 1.25 1.56 0.94 1.25 1.56Re- 35 31 20 34 29 21 33 29 21 action time (min)

Subsequent to completion of polymerisation, emulsions were preparedusing the following process:—

Firstly 1 g water was directly added to the polymerisation product andthe resulting mixture was mixed at 3000 rpm for 60 s. The water additionstep was repeated was repeated with 1 g water added and mixed at 3000rpm for 60 s, then, a further 8 g of water was added and mixed at 3000rpm for 60 s and finally 40 g of water was added and mixed at 1500 μmfor 30 s.

The resulting emulsions were analysed for Molecular weight (obtained byGPC) and cyclic siloxane content (D₄-D₁₂) by gas chromatography. Theresults are provided in Table 13(b) below

TABLE 13(B) Example a b c d e f g h i D(v, 0.1) 0.5 0.33 0.6 0.53 0.360.26 0.21 0.22 0.23 Mm D(v, 0.5) 0.77 2.49 0.99 0.94 1.14 1.7 0.77 1.091.67 Mm D(v, 0.9) 1.05 6.11 1.61 1.48 1.91 3.8 1.91 2.39 4.01 Mm Mn 82158 229 98 162 211 129 174 205 kg/mol Mw 112 220 312 142 229 296 183 252300 kg/mol D₄ (%) 0.06 0.09 0.09 0.07 0.07 0.07 0.05 0.06 0.06 D₅ (%)0.04 0.06 0.06 0.05 0.05 0.05 0.04 0.04 0.04 D₆ (%) 0.05 0.07 0.06 0.060.06 0.05 0.05 0.05 0.05 D₇ (%) 0.06 0.07 0.06 0.07 0.07 0.06 0.06 0.060.05 D₈ (%) 0.05 0.07 0.05 0.06 0.06 0.05 0.05 0.05 0.04 D₉ (%) 0.050.06 0.05 0.06 0.05 0.05 0.05 0.05 0.04 D₁₀ (%) 0.04 0.05 0.04 0.05 0.050.04 0.05 0.05 0.04 D₁₁ (%) 0.04 0.05 0.03 0.04 0.04 0.04 0.04 0.04 0.03D₁₂ (%) 0.04 0.05 0.04 0.04 0.04 0.04 0.04 0.04 0.04

The resulting emulsions prepared in accordance with the above andidentified as Example 13b, Example 13e and Example 13h were introducedinto a selection of personal care formulations, including fruity gelblushers, water in oil and water in silicone skin creams, hair careshampoo, leave-on, and the following:—

Ethnic Hair Care: Conditioner

The above was prepared using the ingredients identified in Table 13(c)below:—

TABLE 13(C) Ingredients INCI Name % Phase A Water 79.47 Natrosol 250 HHRHydroxyethylcellulose 1.5 Arquad 16-29 Cetrimonium Chloride 0.7 Phase BLanette Wax O Cetearyl Alcohol 4 Arlacel 165 Glyceryl Stearate andPEG-100 1 Stearate Phase C Propylene Glycol 4 Glycerin 4 Phase D GluadinW20 Hydrolyzed Wheat Protein 1 Germaben II Propylene Glycol and 1Diazolidinyl Urea and Methylparaben and Propylparaben Phase E Example13e Emulsion 3.33 Viscosity: Spindle 7, 20 rpm 45200 mPa · s

The ingredients of phase A were mixed together and then heated to 75° C.Phase B was then added whilst mixing and the mixture was allowed tocommence cooling. Phase C was then introduced and the resulting mixturewas allowed to cool to 50° C. Phase D was then added and the mixture wascooled to room temperature. Phase E was then added and finally water wasintroduced to compensate for water loss during heating phase.

Several panelists were asked to comb slightly bleached hair tresseswashed with the resulting conditioner to determine the time taken todetangle the wet hair. In comparison the participants had to combslightly bleached hair tresses which had been washed with the sameconditioner formulation without any emulsion. The results indicate asignificant decrease (>99%) into the detangling time when using theconditioner containing example 13e emulsion indicating a positive impacton hair conditioning.

Shower Gel

The above was prepared using the ingredients identified in Table 13(d)below:—

TABLE 13(D) Ingredients INCI Name % Phase A Empicol ESB-3 Sodium LaurethSulfate 30 Oramix NS10 Decyl Glucoside 5 Amonyl 380BA CocamidopropylBetaine 10 Brij 30 Laureth-4 2 Sepigel 305 Polyacrylamide and C13-14 2Isoparaffin and Laureth-7 Water 42.7 Phase B Example 13e Emulsion 8.3Phase C Sodium Chloride q.s Viscosity: Spindle 5, 100 rpm 4000 mPa · s

The ingredients of phase A were initially mixed until homogeneous, afterwhich phase B was introduced whilst mixing was continued. Phase C wasthen introduced to adjust the viscosity of the final mixture to therequired value. It was found that emulsions in accordance with thepresent invention, such as example 13e emulsion, can be easily added toshower gel formulations and provide stable formulations.

Smooth Stay Shadow (Eye Make-Up)

The above was prepared using the ingredients identified in Table 13(e)below:—

TABLE 13(E) Ingredients INCI Name % Phase A Glycerin 8 Propylene Glycol8 Phase B Covacryl RH Sodium Polyacrylate 0.7 Phase C Water 42 NipaguardDMDMH DMDM Hydantoin 0.3 Phase D Example 13b Emulsion 6 Covacryl E14Acrylates Copolymer 20 Phase E Covapearl light brown 830 AS Mica and CI77491 and 4 Triethoxycaprylysilane Covapearl satin 931 AS Mica and CI77891 and 11 Triethoxycaprylysilane

Phase B was first dispersed in phase A. The resulting mixture of PhasesA and B were then mixed into phase C under agitation. Phase D was thenadded to the mixture and was mixed until homogeneous. Finally phase Ewas added and the final formulation was mixed until homogeneous.

It was found that that emulsions such as Example 13b emulsion ashereinbefore described can be easily incorporated into a eye shadowformulations with high pigment levels. 18 panelists compared the eyeshadow formulation with example 13b emulsion in comparison with the sameformulation in the absence of said emulsion. It was identified that theformulation containing Example 13b emulsion increased the tackiness ofthe formulation without significantly impacting the gloss andspreadability of the formulation thereby improving adhesion andretention of the formulation on the skin.

Skinshield—Water in Oil Skin Cream

The above was prepared using the ingredients identified in Table 13(f)below:—

TABLE 13(F) Ingredients INCI Name % Phase A Dow Corning ®5200Formulation Lauryl PEG/PPG-18/18 Methicone 2 Aid Mineral Oil 8 DowCorning ®2-1184 Fluid Trisiloxane and Dimethicone 4.5 Dow Corning ®9040Silicone Cyclopentasiloxane and Dimethicone 5 Elastomemr BlendCrosspolymer Escalol 557 Ethylhexyl Methoxycinnamate 2 Dekaben (as soldby Jan Dekker Phenoxyethanol and Methylparaben and 0.5 company)Ethylparaben and Propylparaben and Butylparaben Phase B Water 61.94Sodium Chloride 1 Propylene Glycol 5 Glycofilm Biosaccharide Gum-4 5Example 13h Emulsion 5 Phase C D&C Red 28 (0.5% in water) D&C red 28/LCW0.06 Viscosity: Spindle 7, 20 rpm 27400 mPa · s

The ingredients of phase A were mixed until homogeneous. The phase Bingredients were then mixed together with sufficient agitation to obtaina homogeneous mixture. Phase C was then introduced into phase B whilstmixing was continued and then the phases B and C mixture was introducedinto phase A whilst mixing. After the complete addition mixing wascontinued for a further 15 minutes

Cold Mix Lotion

The above was prepared using the ingredients identified in Table 13(g)below:—

TABLE 13(G) Ingredients INCI Name % % Phase A Example 13h Emulsion — 20Phase B Water 78 78 Phenochem Phenoxyethanol (and) Methylparaben 1 1(and) Butylparaben (and) Ethylparaben (and) Propylparaben (and)Isobutylparaben Keltrol Xanthan Gum 1 1

The ingredients of phase B were initially mixed together and then theresulting mixture was introduced into phase A and was mixed untilhomogeneous.

Example 14

A polymer was prepared by polymerising a 1:1 mixture of dimethylhydroxyl terminated polydimethylsiloxane having a viscosity of 70 mPa·sat 25° C. and an organic extender (Hydroseal G 250H) using 20 ppm of aphosphonitrile catalyst. The polymerisation was stopped once a viscosityof 100000 mPa·s at 25° C. was reached by the addition of trihexylamine.The polymer had a number average molecular weight of 235000 g/mol and apolydispersity index of 1.48.

1.75 g Volpo® L4, 1.25 g and Volpo® L23 was added to 30 g of thepolymer/extender blend described above and mixed for 20 s at 3000 rpm ina Hausschild dental mixer. An additional 2.0 g of water was added andmixing repeated under the same conditions. Further additions of 2.0 g ofwater were repeated four more times. The resulting mixture was thendiluted with additional 30 g of water.

The above emulsion was evaluated in a fabric softener consisting of:

-   -   55.6 g Tetranyl L1/90 standard    -   8 g MgCl₂.6H₂O solution @ 20%    -   936.4 g of water    -   Total=1000 g→5% active Quat

The Tetranyl L1/90 standard was first melted at 55° C. The resultingliquid was then poured whilst being continuously stirred into in hotwater and the resulting mixture was allowed to cool with continuedstirring. During the cooling period, again with continuous stirring themagnesium chloride salt and the emulsion prepared in accordance with theinvention were introduced.

The fabric (cotton towels) was treated by adding the softener using aMiele washing machine and a washing it with commercial detergent powder(DASH). Softness of towels was determined in a panel test and rated from1-10 (10=softest). While the fabric softener described above was ratedat 5.0, the fabric softener containing the emulsion in accordance withthe present invention was rated at 5.5.

The water absorbency of the treated fabric was tested by dropping a 2cm*2 cm sample into 250 ml water. The time until the fabric is sinkingis recorded. The result was 9 s for the sample treated with softenercontaining the emulsion as described above and 128 s for a sampletreated with a softener only, showing therefore improved waterabsorbency

1-15. (canceled)
 16. A silicone oil-in-water emulsion comprising: aninert organopolysiloxane and/or an organic fluid; and a polysiloxanecontaining polymer comprising the reaction product of siloxanecontaining monomers and/or oligomers in the presence of a catalyst andthe inert fluid; wherein the polysiloxane containing polymer is of thefollowing general formulaR_((3-a))R¹ _(a)SiO[(R₂SiO)_(b)(RR¹SiO)_(c)]SiR_((3-a))R¹ _(a)  (1)wherein each R is the same or different and is an alkyl group containing1 to 8 carbon atoms, a substituted alkyl group containing 1 to 6 carbonatoms, or a phenyl group; R¹ is a hydroxy group, a hydrolysable group,or an unsaturated organic group; a is zero or 1; b is an integer; c iszero or an integer; and the sum of b+c is equal to a value of at least200.
 17. The emulsion according to claim 16, wherein the sum of b+c isequal to a value of at least 500, optionally is equal to a value of atleast
 1500. 18. The emulsion according to claim 16, wherein the inertfluid is retained within the polysiloxane containing polymer in anamount of not more than 70% w/w.
 19. The emulsion according to claim 18,wherein the inert fluid is retained within the polysiloxane containingpolymer in an amount of from 5 to 70% w/w.
 20. The emulsion according toclaim 16, wherein the polysiloxane containing polymer comprises a degreeof branching of less than 10%, optionally a degree of branching of lessthan 2%.
 21. The emulsion according to claim 16, wherein the inert fluidis selected from the group of an organic extender, a plasticizer, anatural oil, and combinations thereof.
 22. The emulsion according toclaim 16, wherein the inert fluid is a cyclic siloxane comprisingbetween 3 to 20 silicon atoms.
 23. The emulsion according to claim 22,wherein the polysiloxane containing polymer is a polydimethyl gum. 24.The emulsion according to claim 16, wherein the inert fluid is atrialkylsilyl terminated polydialkylsiloxane or a derivative thereof,and optionally has a viscosity of from 0.65 to 10000 mPa·s at 25° C. 25.The emulsion according to claim 16, wherein the polysiloxane containingpolymer is prepared via a reaction process selected from the group ofpolycondensation, chain extension, polyaddition, and ring opening. 26.The emulsion according to claim 16, further comprising a surfactant, andoptionally wherein the catalyst is part of the surfactant.
 27. Theemulsion according to claim 26, wherein the polysiloxane containingpolymer is prepared via a polycondensation reaction and the catalyst isdodecylbenzenesulphonic acid.
 28. The emulsion according to claim 16,wherein a homogenous oil phase is from 1000 to 100000 mPa·s at 25° C.29. The emulsion according to claim 16, prepared by a method comprisingthe steps of: (i) preparing the polysiloxane containing polymer by thepolymerization of siloxane containing monomers and/or oligomers in thepresence of the inert fluid and catalyst and optionally an end-blockingagent; (ii) optionally quenching the polymerization process; wherein theinert fluid is retained within the resulting polysiloxane containingpolymer; (iii) optionally introducing one or more surfactants into thepolysiloxane containing polymer to form a homogenous oil phase; (iv)adding water to the homogenous oil phase to form a water-in-oilemulsion, the water being added in an amount of 0.1 to 10 percent byweight based on the total oil phase weight; (v) applying shear to thewater-in-oil emulsion to cause inversion of the water-in-oil emulsion toan oil-in-water emulsion; and (vi) optionally diluting the oil-in-wateremulsion by adding more water.
 30. The emulsion according to claim 29,wherein the sum of b+c is equal to a value of at least 500, optionallyat least
 1500. 31. The emulsion of claim 29, wherein the inert fluid isretained within the polysiloxane containing polymer in an amount of notmore than 70% w/w, optionally in an amount of from 5 to 70% w/w.
 32. Theemulsion according to claim 29, wherein the inert fluid has a viscosityof from 0.65 mPa·s to 10000 mPa·s at 25° C. and is selected from anorganopolysiloxane extender or plasticizer, an organic extender orplasticizer, or a cyclic siloxane comprising between 3 and 20 siliconatoms.
 33. The emulsion according to claim 29, wherein the siloxanecontaining monomers and/or oligomers comprise hydroxyl-terminatedorganopolysiloxanes.
 34. A personal care product comprising the emulsionaccording to claim
 16. 35. The emulsion according to claim 16 in paints,construction applications, textile fibre treatments, leatherlubrication, fabric softening, fabric care for laundry applications,healthcare, homecare, personal care, release agents, water basedcoatings, oil drag reduction, lubrication, and facilitation of cuttingcellulose materials.